CN109331807A - Self-supporting perofskite type oxide nanofiber catalytic purification material and preparation method - Google Patents
Self-supporting perofskite type oxide nanofiber catalytic purification material and preparation method Download PDFInfo
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- CN109331807A CN109331807A CN201811156894.8A CN201811156894A CN109331807A CN 109331807 A CN109331807 A CN 109331807A CN 201811156894 A CN201811156894 A CN 201811156894A CN 109331807 A CN109331807 A CN 109331807A
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- Prior art keywords
- salt
- metal salt
- supporting
- self
- type oxide
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 63
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 61
- 238000000746 purification Methods 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 229920000592 inorganic polymer Polymers 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 22
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 28
- 238000009987 spinning Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- -1 zirconates Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- COWOWCJDIGPUDT-UHFFFAOYSA-N silicic acid;zinc Chemical compound [Zn].[Zn].O[Si](O)(O)O COWOWCJDIGPUDT-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004110 Zinc silicate Substances 0.000 claims 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims 1
- 229940005991 chloric acid Drugs 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000002070 nanowire Substances 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 229960004029 silicic acid Drugs 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 claims 1
- 235000019352 zinc silicate Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 18
- 239000000835 fiber Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 13
- 230000000505 pernicious effect Effects 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 239000013618 particulate matter Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 229910010252 TiO3 Inorganic materials 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000006193 liquid solution Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 1
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- RSDNGLJOQVJZGG-UHFFFAOYSA-L [Zn+2].O.[PH2](=O)[O-].[PH2](=O)[O-] Chemical compound [Zn+2].O.[PH2](=O)[O-].[PH2](=O)[O-] RSDNGLJOQVJZGG-UHFFFAOYSA-L 0.000 description 1
- WBXQXRXMGCOVHA-UHFFFAOYSA-N [methyl(nitroso)amino]methyl acetate Chemical compound O=NN(C)COC(C)=O WBXQXRXMGCOVHA-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- WEUCTTBUEWINIJ-UHFFFAOYSA-N acetic acid;zinc;dihydrate Chemical compound O.O.[Zn].CC(O)=O WEUCTTBUEWINIJ-UHFFFAOYSA-N 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- HVXCTUSYKCFNMG-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical class [O-2].[Zr+4].[Al+3] HVXCTUSYKCFNMG-UHFFFAOYSA-N 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 235000013495 cobalt Nutrition 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- RSJOBNMOMQFPKQ-ZVGUSBNCSA-L copper;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O RSJOBNMOMQFPKQ-ZVGUSBNCSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960002413 ferric citrate Drugs 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical class [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 150000004690 nonahydrates Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0001—Making filtering elements
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention discloses a kind of self-supporting perofskite type oxide nanofiber catalytic purification materials, it is made of element A metal salt, B element metal salt and inorganic polymer flocculant, element A metal salt, B element metal salt collectively constitute metal salt, and the total molar ratio with inorganic polymer flocculant of metal salt is 1:0.001-0.05.The invention also discloses a kind of preparation methods of self-supporting perofskite type oxide nanofiber catalytic purification material, step includes: 1) to hydrolyze element A metal salt and B element metal salt together, form perofskite type oxide nano colloidal particles, it adds inorganic polymer flocculant to stir evenly, obtains precursor solution；2) presoma nanofiber is made using electrostatic spinning process in precursor solution；3) presoma nanofiber is calcined in air atmosphere, obtains self-supporting perofskite type oxide nanofiber catalytic purification material.Low manufacture cost of the invention, filter effect are good.
Description
Technical field
The invention belongs to technical field of new material preparation, are related to a kind of self-supporting perofskite type oxide nanofiber catalysis
Scavenging material, the invention further relates to the preparation methods of this kind of self-supporting perofskite type oxide nanofiber catalytic purification material.
Background technique
In recent years, as growing rapidly for economy is highly developed with industry, problem of environmental pollution is increasingly severe, wherein
Air pollutants mainly from factory, automobile, power plant discharge harmful gas such as nitric oxide, carbon monoxide and hydrogen sulfide
Body has an important influence on people's quality of life and the general level of the health, and therefore, exploitation is efficient and can remove above-mentioned pernicious gas simultaneously
Multiple-effect catalyst be increasingly valued by people.The multiple-effect catalyst being commonly used is essentially all using noble metal
For active component, although catalytic performance is preferable, noble metal is expensive to be difficult to be widely applied, thus develop it is cheap, can
The perovskite-type oxide catalysts promoted on a large scale become current research hotspot.
Perofskite type oxide general molecular formula is ABO3, wherein A are the thulium with larger ionic radius
Or alkali earth metal, it can be coordinated with 12 oxygen, positioned at the center of cube；The B generally lesser transition of ionic radius are golden
Belong to element, can be coordinated with 6 oxygen, positioned at the apex angle of cube.Perofskite type oxide has unique crystal structure, this knot
Structure can control the activity of oxygen vacancies and its content, oxygen in lattice, and redox and the heat for increasing substantially catalyst are steady
It is qualitative, therefore perovskite can substitute noble metal active component in many fields and use, price advantage is obvious, can be widely applied.
Chinese patent CN101745405A discloses the catalyst of the perofskite type oxide of purification of exhaust gases of internal combustion engines, adopts
Catalyst is prepared with gel technique, which is powder structure, it is difficult to recycling and recycling difficulty.Chinese patent
CN107876066A discloses a kind of preparation method and applications of palladium-iridium bimetallic alloy perovskite auto-exhaust catalyst,
The catalyst improves the catalytic performance of catalyst by adjusting bimetallic synergistic effect, but needs that your gold is added in preparation process
Belong to, preparation process is complicated, high production cost, it is difficult to be widely applied.Permitted to open and the paper of Wang Bingquan " diesel engine vent gas purification use
Perovskite type catalyst research " [Chongqing Environmental Science, 1993 (6): 10-15], disclose and utilize infusion process preparation different
The perovskite type catalyst of type, by γ-Al2O3With γ-Al2O3The ceramic honeycomb of cordierite structure does carrier, according to ABO3Chemistry
The configuration of metering prepares perovskite type catalyst, this method preparation at certain density active component solution, by multiple maceration
Catalyst there is preferable low temperature active, however the complex technical process, drying process will lead to active component migration, reduce
Fiber catalytic efficiency.
Summary of the invention
The object of the present invention is to provide a kind of self-supporting perofskite type oxide nanofiber catalytic purification materials, solve
The high production cost of the prior art, complex technical process, the relatively low problem of fiber catalytic efficiency.
It is a further object of the present invention to provide this kind of self-supporting perofskite type oxide nanofiber catalytic purification materials
Preparation method.
The technical scheme adopted by the invention is that a kind of self-supporting perofskite type oxide nanofiber catalytic purification material
Material, is made of element A metal salt, B element metal salt and inorganic polymer flocculant, and element A metal salt, B element metal salt are total
With composition metal salt, the total molar ratio with inorganic polymer flocculant of metal salt is 1:0.001-0.05.
Another technical solution of the present invention is, a kind of above-mentioned self-supporting perofskite type oxide nanofiber is urged
The preparation method for changing scavenging material, follows the steps below to implement:
Step 1: element A metal salt and B element metal salt being hydrolyzed together, form perofskite type oxide nanometre glue
Grain is then added inorganic polymer flocculant and stirs evenly, obtains the precursor solution of stable homogeneous；Wherein element A metal salt
It is 1:0.001-0.05 with the total molar ratio with inorganic polymer flocculant of B element metal salt；
Element A metal salt and the hydrolysis of B element metal salt refer to that strong base-weak acid salt stirs 30- under the conditions of pH is 3-5
180min is hydrolyzed or strong acid weak base salt stirring 30-180min under the conditions of pH is 10-12 is hydrolyzed, and forms perovskite
Type oxidate nano micelle；Mixing time after inorganic polymer flocculant is added is 10-120min；
Step 2: presoma nanofiber is made using electrostatic spinning process in above-mentioned precursor solution；
Step 3: above-mentioned presoma nanofiber being calcined in air atmosphere, self-supporting perofskite type oxide is obtained and receives
Rice fiber catalytic purification material.
The invention has the advantages that element A metal salt and B element metal salt are hydrolyzed to form Ca-Ti ore type oxidation first
Object nano colloidal particles are then added inorganic polymer flocculant and stir evenly, perofskite type oxide nano colloidal particles and inorganic high score
The precursor solution of stable homogeneous is formed between sub- flocculant by hydrogen bond action, has in the precursor solution and stablizes three-dimensional interlocking
The strand of reticular structure；It is not necessary that organic high molecular polymer is added in the precursor solution, Ca-Ti ore type is significantly improved
The yield of oxide fibre, the perofskite type oxide nanofiber catalytic purification material finally prepared show preferable flexibility
And tensile strength.The self-supporting perofskite type oxide nanofiber catalytic purification material is while being catalytically decomposed pernicious gas
Particulate pollutant can be effectively filtered, to the removal rate of pernicious gas up to 95% or more, to 0.02~10 μm of particulate matter of partial size
For filter efficiency up to 99.99% or more, resistance pressure drop is less than 200Pa.
Detailed description of the invention
Fig. 1 is self-supporting Ca-Ti ore type La prepared by the embodiment of the present invention 10.4Ce0.6CoO3Nanofiber catalytic purification material
The micrograph of material.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Self-supporting perofskite type oxide nanofiber catalytic purification material of the invention, by element A metal salt, B element
Metal salt and inorganic polymer flocculant form, and element A metal salt, B element metal salt collectively constitute metal salt, and metal salt is total
Molar ratio with inorganic polymer flocculant is 1:0.001-0.05.
The preparation method of self-supporting perofskite type oxide nanofiber catalytic purification material of the invention, according to following step
It is rapid to implement:
Step 1: element A metal salt and B element metal salt being hydrolyzed together, form perofskite type oxide nanometre glue
Grain is then added inorganic polymer flocculant and stirs evenly, and obtains the precursor solution of stable homogeneous, which moves
Power viscosity is 0.05Pas-5Pas；
Wherein element A metal salt and the total molar ratio with inorganic polymer flocculant of B element metal salt are 1:0.001-
0.05；Element A metal salt and the hydrolysis of B element metal salt refer to that strong base-weak acid salt stirs 30- under the conditions of pH is 3-5
180min is hydrolyzed or strong acid weak base salt stirring 30-180min under the conditions of pH is 10-12 is hydrolyzed, and forms perovskite
Type oxidate nano micelle, colloid size 1-60nm；Mixing time after inorganic polymer flocculant is added is 10-
120min；
The chemical general formula of perofskite type oxide is ABO3, wherein A for La, Ce, Pr, Nd, Sm, Y, Sc, Be, Ca, Sr,
One of the rare earth elements or alkaline earth element such as Ba or multiple combinations；The corresponding nitrate of element A metal salt selection rare earth element,
One of sulfate and the corresponding nitrate of alkaline earth element, chlorate, perchlorate, acetate or multiple combinations；B are
One of transition metal elements such as Mn, Ti, Fe, Co, Ni, Cr or multiple combinations；B element metal salt selects manganese salt, mantoquita, iron
One of salt, titanium salt, zirconates, cobalt salt, nickel salt, aluminium salt, chromic salts, pink salt, zinc salt or multiple combinations；
Manganese salt selects manganese acetylacetonate, manganese acetate, manganese chloride, four hydrated manganese sulfates or manganese nitrate；
Mantoquita selects Salzburg vitriol, copper nitrate, cupric tartrate, basic copper carbonate, copper chloride or copper citrate；
Molysite selects ferrocene, ferric acetyl acetonade, six ferrous sulfate hydrate ammoniums, ferric trichloride or ferric citrate amine；
Titanium salt selects titanium tetrachloride, isopropyl titanate, butyl titanate or titanyl sulfate；
Zirconates selects zirconium acetate, zirconium chloride, acetylacetone,2,4-pentanedione zirconium, eight hydrated aluminum zirconium oxides, zirconyl nitrate or zirconium-n-propylate；
Cobalt salt selects acetylacetone cobalt, eight nitric hydrate cobalts, cobalt chloride hexahydrate, cobalt acetate or cobalt oxalate；
Nickel salt selects nickel nitrate, nickel oxalate, nickel sulfate hexahydrate, nickel chloride or nickel acetylacetonate；
Aluminium salt selects Aluminium chloride hexahydrate, aluminium isopropoxide, aluminium acetylacetonate or ANN aluminium nitrate nonahydrate；
Chromic salts selects chromium acetate, chromium sulfate, Hexaaquachromium chloride or Chromium nitrate (Cr(NO3)3),nonahydrate；
Pink salt selects tin tetrachloride, stannous sulfate or tributyltin chloride；
Zinc salt select zinc acetylacetonate, zinc chloride, Zinc vitriol, zinc dimethacrylate, acetic acid dihydrate zinc or
Six hypophosphite monohydrate zinc.
Inorganic polymer flocculant selects aluminium polychloride, polyaluminium sulfate, poly-ferric chloride, bodied ferric sulfate, polymerization
Alumina silicate, polyferric silicate sulfate, poly- phosphorus aluminium chloride, polysilicate aluminum chloride, polyaluminum sulfate aluminium chloride, polymeric aluminum sulfate silicate, polysilicate ferric chloride
Or one of polymeric silicicacid zinc.
Step 2: presoma nanofiber is made using electrostatic spinning process in above-mentioned precursor solution,
When spinneret tip drop charge repulsion is more than its surface tension, the jet stream that droplet surface ejects passes through electric field
High-speed stretch, the solvent volatilization of power, final solidification deposition on the reception device, obtain presoma nanofiber, which receives
The uniform diameter of rice fiber, continuity are good；
Electrostatic spinning process parameter is, under conditions of 10 DEG C -30 DEG C of temperature and relative humidity 20%-75%, by forerunner
Liquid solution carries out spinning with the rate of flooding of 0.1mL/h-6mL/h, and distance is 15cm-30cm between reception device and spinning head,
It is 10kV-30kV that spinning head, which applies voltage,.
Step 3: above-mentioned presoma nanofiber being calcined in air atmosphere, calcination temperature gradually rises to 800 from room temperature
DEG C -1200 DEG C, heating rate is 1 DEG C/min-5 DEG C/min, keeps 30-120min in highest calcination temperature, obtains self-supporting
Perofskite type oxide nanofiber catalytic purification material.The self-supporting perofskite type oxide nanofiber catalytic purification material
Average fibre diameter be 10nm-900nm, the specific surface area of tunica fibrosa is 30m2/g-200m2/g；The self-supporting Ca-Ti ore type oxygen
The tensile strength of compound nanofiber catalytic purification material is 5MPa-500MPa.
Inorganic polymer flocculant is primarily used to Treatment of Industrial Water field at present, by the hydroxyl and water on its surface
Larger size impurity particle (including colloidal particles, dyestuff and larger blocky particulate matter etc.) occurs adherency, builds bridge and be crosslinked and make
With and reach the flocculating result of impurity, the final purpose for realizing purification of water quality.But the inorganic polymer in preparation method of the present invention
Hydrogen bond action only has occurred between flocculant and perofskite type oxide nano colloidal particles and is formed and stablizes three-dimensional interlocking reticular structure point
Subchain, this is because in precursor solution of the invention perofskite type oxide nano colloidal particles having a size of nanometer scale, and
Respectively less than 100nm, while nano colloidal particles enormous amount reach several hundred million, after minimal amount of inorganic polymer flocculant is added, calcium
Hydrogen Binding Adsorption effect, nanometre glue occur between the oxidate nano micelle meeting of titanium ore type and the hydroxyl on inorganic polymer flocculant surface
The fully wrapped around firmly inorganic polymer flocculant of grain meeting is formed, other hydroxyls on nano colloidal particles surface can also adsorb other inorganic height
Molecular flocculant molecule ultimately forms and stablizes three-dimensional interlocking reticular structure strand, big due to nano colloidal particles in the process
Amount exists so that coagulating sedimentation effect can not occur between inorganic polymer flocculant, therefore obtain uniform and have certain glutinous
The spinnable precursor solution of degree, so that presoma nanofiber is uniform, continuity is preferable.
Embodiment 1
Prepare self-supporting Ca-Ti ore type La0.4Ce0.6CoO3Nanofiber catalytic purification material.
Step 1: by lanthanum nitrate, cerous nitrate and cobalt chloride hexahydrate, stirring 60min completes hydrolysis under conditions of pH is 11,
Form complex hydroxide nano colloidal particles, particle median diameter 30nm；Inorganic macromolecule flocculant poly sulfuric acid is then added
Iron, then persistently stir 50min；
Wherein the molar ratio of lanthanum nitrate, cerous nitrate and cobalt chloride hexahydrate is 20:30:50, and metal salt adds up to and inorganic height
The molar ratio of molecular flocculant bodied ferric sulfate is 1:0.05；Being uniformly mixed and the dynamic viscosity of stable homogeneous is made is 0.05Pa
The precursor solution of s.Strand has lanthanum hydroxide, cerium hydroxide and cobalt hydroxide nano colloidal particles and inorganic in precursor solution
What macromolecule flocculant poly ferric sulfate long-chain was formed stablizes three-dimensional interlocking reticular structure, and structural formula is as follows:
Embodiment 1 stablizes three-dimensional interlocking reticular structure formula
Step 2: presoma nanofiber is made using electrostatic spinning process in above-mentioned precursor solution；
Electrostatic spinning process parameter is: spinning temperature is 10 DEG C, relative humidity 50%, and rate of flooding 3.5mL/h is received
Distance is 26cm, spinning voltage 23kV；
Step 3: above-mentioned presoma nanofiber being calcined in air atmosphere, calcination temperature gradually rises to 1100 from room temperature
DEG C, heating rate is 4 DEG C/min, and keeps 100min in highest calcination temperature, obtains self-supporting La0.4Ce0.6CoO3It receives
Rice fiber catalytic purification material.
It referring to Fig.1, is the self-supporting Ca-Ti ore type La of the preparation of the embodiment of the present invention 10.4Ce0.6CoO3Nanofiber catalysis is net
Change the micrograph of material.Self-supporting La0.4Ce0.6CoO3The average fibre diameter of nanofiber catalytic purification material be 600nm,
Specific surface area is 180m2/ g, the tensile strength of nanofiber catalytic purification material are 500MPa.
Self-supporting La0.4Ce0.6CoO3Nanofiber catalytic purification material while pernicious gas is catalytically decomposed for having
Effect filtering particulate pollutant, the removal rate to 0.3wt% hydrogen sulfide gas is 95.8%, to 0.03~8 μm of particulate matter of partial size
Filter efficiency is 99.996%, resistance pressure drop 108Pa.
Embodiment 2
Prepare self-supporting Ca-Ti ore type LaFe0.8Al0.2O3Nanofiber catalytic purification material.
Step 1: lanthanum sulfate, six ferrous sulfate hydrate ammoniums and ANN aluminium nitrate nonahydrate are stirred under conditions of pH is 12 together
180min completes hydrolysis, forms complex hydroxide nano colloidal particles, particle median diameter 1nm；Inorganic polymer is then added
Flocculant poly aluminum sulfate, then persistently stir 85min；
The wherein molar ratio 50:40:10 of lanthanum sulfate, six ferrous sulfate hydrate ammoniums and ANN aluminium nitrate nonahydrate, metal salt are total
Molar ratio with polyaluminium sulfate is 1:0.012；It is uniformly mixed the forerunner for being made that the dynamic viscosity of stable homogeneous is 0.8Pas
Liquid solution.Strand has lanthanum hydroxide, iron hydroxide and nano aluminum hydroxide gel grain and polyaluminium sulfate in precursor solution
What long-chain was formed stablizes three-dimensional interlocking reticular structure, and structural formula is as follows:
Embodiment 2 stablizes three-dimensional interlocking reticular structure formula
Step 2: presoma nanofiber is made using electrostatic spinning process in above-mentioned precursor solution；
Electrostatic spinning process parameter is: spinning temperature is 25 DEG C, relative humidity 58%, and rate of flooding 0.8mL/h is received
Distance is 15cm, spinning voltage 30kV；
Step 3: above-mentioned presoma nanofiber being calcined in air atmosphere, calcination temperature gradually rises to 900 from room temperature
DEG C, heating rate is 3 DEG C/min, and keeps 55min in highest calcination temperature, obtains self-supporting LaFe0.8Al0.2O3Nanometer
Fiber catalytic purification material.
Self-supporting LaFe0.8Al0.2O3The average fibre diameter of nanofiber catalytic purification material is 10nm, specific surface area
170m2/ g, the tensile strength of nanofiber catalytic purification material are 260MPa.
Self-supporting LaFe0.8Al0.2O3Nanofiber catalytic purification material while pernicious gas is catalytically decomposed for having
Effect filtering particulate pollutant, the removal rate to 1wt% sulfur dioxide gas is 98.3%, to 0.05~6 μm of particulate matter of partial size
Filter efficiency is 99.995%, resistance pressure drop 174Pa.
Embodiment 3
Prepare self-supporting Ca-Ti ore type Ce0.9Y0.1Mn0.7Cu0.3O3Nanofiber catalytic purification material.
Step 1: by cerous nitrate and yttrium nitrate, stirring 30min completes hydrolysis under conditions of pH is 10 together, forms hydrogen-oxygen
Change cerium and yttrium hydroxide nano colloidal particles；Meanwhile stirring 50min completes hydrolysis under conditions of pH is 3 by manganese acetate and copper nitrate,
Manganous hydroxide and Kocide SD nano colloidal particles are formed, then are mixed to form complex hydroxide nano colloidal particles jointly, micelle is average straight
Diameter is 60nm；Inorganic polymer flocculant polysilicate aluminum chloride is then added, then persistently stirs 45min；Wherein cerous nitrate and nitric acid
The molar ratio of yttrium, manganese acetate and copper nitrate is 90:10:70:30, and the total molar ratio with polysilicate aluminum chloride of metal salt is 1:
0.021；It is uniformly mixed the precursor solution for being made that the dynamic viscosity of stable homogeneous is 5Pas, strand in the precursor solution
Stablize three-dimensional interlocking reticular structure with similar with embodiment 1；
Step 2: presoma nanofiber is made using electrostatic spinning process in above-mentioned precursor solution；
Electrostatic spinning process parameter is: spinning temperature is 20 DEG C, relative humidity 42%, and rate of flooding 0.1mL/h is received
Distance is 20cm, spinning voltage 25kV；
Step 3: above-mentioned presoma nanofiber being calcined in air atmosphere, calcination temperature gradually rises to 1000 from room temperature
DEG C, heating rate is 2 DEG C/min, and keeps 80min in highest calcination temperature, obtains self-supporting
Ce0.9Y0.1Mn0.7Cu0.3O3Nanofiber catalytic purification material.
Self-supporting Ce0.9Y0.1Mn0.7Cu0.3O3The average fibre diameter of nanofiber catalytic purification material is 850nm, compares
Surface area 135m2/ g, the tensile strength of nanofiber catalytic purification material are 345MPa.
Self-supporting Ce0.9Y0.1Mn0.7Cu0.3O3Nanofiber catalytic purification material is for being catalytically decomposed the same of pernicious gas
Shi Youxiao filters particulate pollutant, and the removal rate to 0.5wt% nitric oxide gas is 96%, to 0.03~7 μm of particle of partial size
The filter efficiency of object is 99.994%, resistance pressure drop 135Pa.
Embodiment 4
Prepare self-supporting Ca-Ti ore type Y0.6Sr0.4TiO3Nanofiber catalytic purification material.
Step 1: by yttrium nitrate and strontium nitrate, stirring 85min completes hydrolysis under conditions of pH is 11 together, forms hydrogen-oxygen
Change yttrium and strontium hydroxide nano colloidal particles；Meanwhile by isopropyl titanate, stirring 80min completes hydrolysis under conditions of pH is 4, then altogether
It is same to be mixed to form complex hydroxide nano colloidal particles, particle median diameter 25nm；It is poly- that inorganic polymer flocculant is then added
Aluminium chloride is closed, then persistently stirs 100min；Wherein the molar ratio of yttrium nitrate, strontium nitrate and isopropyl titanate is 30:20:50, gold
Belonging to the total molar ratio with aluminium polychloride of salt is 1:0.001；It is uniformly mixed and the dynamic viscosity of stable homogeneous is made is
The precursor solution of 0.36Pas, strand, which has, in the precursor solution similar with embodiment 2 stablizes three-dimensional mutual lock network
Shape structure；
Step 2: presoma nanofiber is made using electrostatic spinning process in above-mentioned precursor solution；
Electrostatic spinning process parameter is: spinning temperature is 26 DEG C, relative humidity 75%, and rate of flooding 2.4mL/h is received
Distance is 28cm, spinning voltage 20kV；
Step 3: above-mentioned presoma nanofiber being calcined in air atmosphere, calcination temperature gradually rises to 800 from room temperature
DEG C, heating rate is 1 DEG C/min, and keeps 90min in highest calcination temperature, obtains self-supporting Y0.6Sr0.4TiO3Nanometer
Fiber catalytic purification material.
Self-supporting Y0.6Sr0.4TiO3The average fibre diameter of nanofiber catalytic purification material is 540nm, specific surface area
For 80m2/ g, the tensile strength of nanofiber catalytic purification material are 5MPa.
Self-supporting Y0.6Sr0.4TiO3Nanofiber catalytic purification material is effective while pernicious gas for being catalytically decomposed
Particulate pollutant is filtered, the removal rate to 0.8wt% CO gas is 97.3%, to 0.02~5 μm of particulate matter of partial size
Filter efficiency is 99.999% or more, resistance pressure drop 45Pa.
Embodiment 5
Prepare self-supporting Ca-Ti ore type BaCr0.2Zn0.8O3Nanofiber catalytic purification material.
Step 1: by barium acetate, chromium acetate and zinc acetylacetonate, stirring 120min completes water under conditions of pH is 5 together
Solution forms complex hydroxide nano colloidal particles, particle median diameter 50nm；Inorganic macromolecule flocculant poly chlorine is then added
Change iron, then persistently stirs 60min；Wherein the molar ratio of chromium acetate, zinc acetylacetonate and barium acetate is 10:40:50, and metal salt closes
The molar ratio of meter and poly-ferric chloride is 1:0.006；The dynamic viscosity that stable homogeneous is made is uniformly mixed as before 0.43Pas
Liquid solution is driven, there is strand the stablize solid similar with embodiment 1 to interlock reticular structure in the precursor solution；
Step 2: presoma nanofiber is made using electrostatic spinning process in above-mentioned precursor solution；
Electrostatic spinning process parameter is: spinning temperature be 18 DEG C, relative humidity 46%, rate of flooding 6mL/h, receive away from
From for 30cm, spinning voltage 22kV；
Step 3: above-mentioned presoma nanofiber being calcined in air atmosphere, calcination temperature gradually rises to 1000 from room temperature
DEG C, heating rate is 3 DEG C/min, and keeps 120min in highest calcination temperature, obtains self-supporting BaCr0.2Zn0.8O3It receives
Rice fiber catalytic purification material.
Self-supporting BaCr0.2Zn0.8O3The average fibre diameter of nanofiber catalytic purification material is 900nm, specific surface
Product is 160m2/ g, the tensile strength of nanofiber catalytic purification material are 205MPa.
Self-supporting BaCr0.2Zn0.8O3Nanofiber catalytic purification material while pernicious gas is catalytically decomposed for having
Effect filtering particulate pollutant, the removal rate to 1wt% sulfur dioxide gas is 96.8%, to 0.03~10 μm of particulate matter of partial size
Filter efficiency is 99.991%, resistance pressure drop 89Pa.
Embodiment 6
Prepare self-supporting Ca-Ti ore type La0.7Ca0.3Sn0.9Zr0.1O3Nanofiber catalytic purification material.
Step 1: lanthanum nitrate, calcium nitrate, tin tetrachloride and titanium tetrachloride are stirred under conditions of pH is 10 together
145min completes hydrolysis, forms complex hydroxide nano colloidal particles, particle median diameter 45nm；Inorganic polymer is then added
The poly- phosphorus aluminium chloride of flocculant, then persistently stir 5min；The wherein molar ratio of lanthanum nitrate, calcium nitrate, tin tetrachloride and titanium tetrachloride
For 70:30:90:10, the total molar ratio with poly- phosphorus aluminium chloride of metal salt is 1:0.017；It is uniformly mixed and stable homogeneous is made
Dynamic viscosity is the precursor solution of 0.25Pas, and strand has the stabilization similar with embodiment 2 in the precursor solution
Solid interlocking reticular structure；
Step 2: presoma nanofiber is made using electrostatic spinning process in above-mentioned precursor solution；
Electrostatic spinning process parameter is: spinning temperature is 30 DEG C, relative humidity 20%, and rate of flooding 1.4mL/h is received
Distance is 18cm, spinning voltage 10kV；
Step 3: above-mentioned presoma nanofiber being calcined in air atmosphere, calcination temperature gradually rises to 1200 from room temperature
DEG C, heating rate is 5 DEG C/min, and keeps 30min in highest calcination temperature, obtains self-supporting
La0.7Ca0.3Sn0.9Zr0.1O3Nanofiber catalytic purification material.
Self-supporting La0.7Ca0.3Sn0.9Zr0.1O3The average fibre diameter of nanofiber catalytic purification material be 485nm,
Specific surface area is 200m2/ g, the tensile strength of nanofiber catalytic purification material are 385MPa.
Self-supporting La0.7Ca0.3Sn0.9Zr0.1O3Nanofiber catalytic purification material is for being catalytically decomposed pernicious gas
Particulate pollutant is effectively filtered simultaneously, and the removal rate to 0.6wt% nitric oxide gas is 99%, to partial size 0.03~9 μm
The filter efficiency of grain object is 99.996%, resistance pressure drop 75Pa.
Claims (8)
1. a kind of self-supporting perofskite type oxide nanofiber catalytic purification material, it is characterised in that: by element A metal salt, B
Metal element salt and inorganic polymer flocculant form, and element A metal salt, B element metal salt collectively constitute metal salt, metal salt
Total molar ratio with inorganic polymer flocculant is 1:0.001-0.05.
2. self-supporting perofskite type oxide nanofiber catalytic purification material according to claim 1, it is characterised in that:
The element A metal salt selects the corresponding nitrate of rare earth element, sulfate and the corresponding nitrate of alkaline earth element, chloric acid
One of salt, perchlorate, acetate or multiple combinations.
3. self-supporting perofskite type oxide nanofiber catalytic purification material according to claim 1, it is characterised in that:
The B element metal salt select manganese salt, mantoquita, molysite, titanium salt, zirconates, cobalt salt, nickel salt, aluminium salt, chromic salts, pink salt, in zinc salt
One or more combinations.
4. self-supporting perofskite type oxide nanofiber catalytic purification material according to claim 1, it is characterised in that:
The inorganic polymer flocculant selects aluminium polychloride, polyaluminium sulfate, poly-ferric chloride, bodied ferric sulfate, polymerization silicon
Sour aluminium, polyferric silicate sulfate, poly- phosphorus aluminium chloride, polysilicate aluminum chloride, polyaluminum sulfate aluminium chloride, polymeric aluminum sulfate silicate, polysilicate ferric chloride or
One of polymeric silicicacid zinc.
5. a kind of preparation of any self-supporting perofskite type oxide nanofiber catalytic purification material of claim 1-4
Method, which is characterized in that follow the steps below to implement:
Step 1: element A metal salt and B element metal salt are hydrolyzed together, form perofskite type oxide nano colloidal particles,
Inorganic polymer flocculant is then added to stir evenly, obtains the precursor solution of stable homogeneous；Wherein element A metal salt and B
The total molar ratio with inorganic polymer flocculant of metal element salt is 1:0.001-0.05；
Element A metal salt and the hydrolysis of B element metal salt refer to that strong base-weak acid salt stirs 30-180min under the conditions of pH is 3-5
It is hydrolyzed or strong acid weak base salt stirring 30-180min under the conditions of pH is 10-12 is hydrolyzed, form Ca-Ti ore type oxidation
Object nano colloidal particles；Mixing time after inorganic polymer flocculant is added is 10-120min；
Step 2: presoma nanofiber is made using electrostatic spinning process in above-mentioned precursor solution；
Step 3: above-mentioned presoma nanofiber being calcined in air atmosphere, obtains self-supporting perofskite type oxide Nanowire
Tie up catalytic purification material.
6. the preparation method of self-supporting perofskite type oxide nanofiber catalytic purification material according to claim 5,
It is characterized by: element A metal salt selects the corresponding nitrate of rare earth element, sulfate and alkaline earth element in the step 1
One of corresponding nitrate, chlorate, perchlorate, acetate or multiple combinations；B element metal salt selects manganese salt, copper
One of salt, molysite, titanium salt, zirconates, cobalt salt, nickel salt, aluminium salt, chromic salts, pink salt, zinc salt or multiple combinations；
Inorganic polymer flocculant selects aluminium polychloride, polyaluminium sulfate, poly-ferric chloride, bodied ferric sulfate, polymeric silicicacid
Aluminium, polyferric silicate sulfate, poly- phosphorus aluminium chloride, polysilicate aluminum chloride, polyaluminum sulfate aluminium chloride, polymeric aluminum sulfate silicate, polysilicate ferric chloride or poly-
Close one of zinc silicate.
7. the preparation method of self-supporting perofskite type oxide nanofiber catalytic purification material according to claim 5,
It is characterized by: electrostatic spinning process parameter is, in 10 DEG C -30 DEG C of temperature and relative humidity 20%- in the step 2
Under conditions of 75%, precursor solution is subjected to spinning with the rate of flooding of 0.1mL/h-6mL/h, reception device and spinning head it
Between distance be 15cm-30cm, spinning head apply voltage be 10kV-30kV.
8. the preparation method of self-supporting perofskite type oxide nanofiber catalytic purification material according to claim 5,
It is characterized by: in the step 3, calcination temperature gradually rises to 800 DEG C -1200 DEG C from room temperature, heating rate is 1 DEG C/
Min-5 DEG C/min, 30-120min is kept in highest calcination temperature.
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